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WO2015109066A1 - Production de films de poly alpha-1,3-glucane formiate - Google Patents

Production de films de poly alpha-1,3-glucane formiate Download PDF

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Publication number
WO2015109066A1
WO2015109066A1 PCT/US2015/011551 US2015011551W WO2015109066A1 WO 2015109066 A1 WO2015109066 A1 WO 2015109066A1 US 2015011551 W US2015011551 W US 2015011551W WO 2015109066 A1 WO2015109066 A1 WO 2015109066A1
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WIPO (PCT)
Prior art keywords
film
glucan
poly alpha
formate
solution
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Ceased
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PCT/US2015/011551
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English (en)
Inventor
T. Joseph Dennes
Debora Flanagan Massouda
Vindhya Mishra
Andrea M. PERTICONE
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US15/110,272 priority Critical patent/US10106626B2/en
Publication of WO2015109066A1 publication Critical patent/WO2015109066A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

Definitions

  • This invention relates to poly alpha-1 ,3-glucan formate films and poly alpha-1 ,3-glucan films and methods of their preparation.
  • Glucose-based polysaccharides and their derivatives can be of potential industrial application.
  • Cellulose is a typical example of such a polysaccharide and is comprised of beta-1 ,4-D-glycosidic linkages of hexopyranose units.
  • Cellulose is used for several commercial applications such as in manufacture of fibers and films (cellophane).
  • Cellulose for industrial applications is derived from wood pulp. Solutioning of wood pulp is a difficult procedure.
  • the most commonly used process for dissolution of cellulose is the 'viscose process' where the cellulose is converted to cellulose xanthate made by treating a cellulose compound with sodium hydroxide and carbon disulfide. The cellulose xanthate solution is extruded into a coagulation bath, where it is regenerated upon coagulation to form a cellulose film.
  • Cellophane film has several desirable attributes like clarity, barrier to oxygen, mechanical strength etc which has resulted in its application as a packaging film.
  • the disadvantage is the use of this viscose process in
  • a widely used process for the preparation of cellulose acetate as described in US Patent 2478425 A comprises (1 ) a pretreatment step (activating step) of mixing a cellulose material having a high a-cellulose content with a small amount of an acid, (2) an acetylating step of treating the pretreated cellulose material with a mixed acid of acetic anhydride, acetic acid and an acidic catalyst, such as sulfuric acid, to obtain primary cellulose acetate, (3) a ripening step of hydrolyzing, according to need, the primary cellulose acetate obtained by the acetylation step to obtain cellulose acetate or cellulose acetate having a higher acetylation degree and (4) a purifying step of separating and purifying the obtained cellulose acetate by precipitation, solid-liquid separation, washing
  • the hydrolysis is ordinarily conducted for a very long time at a temperature slightly higher than ambient temperature, but lower than 40°C.
  • a cellulose starting material having a very high quality and a high a-cellulose content should be used.
  • wood pulp there is a quality standard for the acetate grade wood pulp.
  • Films of cellulose acetate can be prepared by either by melt extrusion methods or by casting methods. For many reasons, however, films prepared by melt extrusion are generally not suitable for optical applications such as for protective covers and substrates in electronic displays. Rather, casting methods are almost exclusively used to manufacture films for optical applications. Casting methods involve first dissolving the polymer in an appropriate solvent to form a dope having a high viscosity, and then applying the viscous dope to a continuous highly polished metal band or drum through an extrusion die, partially drying the wet film, peeling the partially dried film from the metal support, and conveying the partially dried film through an oven to more completely remove solvent from the film.
  • glucan polymers with alpha- 1 ,3-glycoside linkages, have been shown to possess significant
  • U.S. Patent No. 7,000,000 disclosed preparation of a polysaccharide fiber comprising a polymer with hexose units, wherein at least 50% of the hexose units within the polymer were linked via alpha-1 ,3- glycoside linkages, and a number average degree of polymerization of at least 100.
  • a glucosyltransferase enzyme from Streptococcus salivarius (gtfJ) was used to produce the polymer.
  • the polymer alpha-1 ,3-glucan was acetylated in order to render the polymer soluble in the spinning solvent.
  • the acetylated polymer was then dissolved in a mixture of trifluoro-acetic acid and dichloromethane. From this solution continuous, strong, fibers of glucan acetate were spun. These glucan acetate fibers can subsequently be de-acetylated to form fibers composed of alpha-1 ,3- glucan.
  • the present invention is directed toward a film comprising poly alpha-1 ,3-glucan formate.
  • the present invention is also directed toward a process for making a poly alpha-1 ,3-glucan formate film comprising: (a) dissolving poly alpha-
  • the present invention is directed toward a film comprising poly alpha-1 ,3-glucan.
  • the present invention is also directed toward a process for making a poly alpha-1 ,3-glucan film comprising: (a) dissolving poly alpha-1 ,3- glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate; (b) contacting the solution of poly alpha- 1 ,3-glucan formate with a surface; (c) removing the solvent composition to form a poly alpha-1 ,3-glucan formate film; and (d) removing the formate in the poly alpha-1 ,3-glucan formate film to form the poly alpha-1 ,3-glucan film.
  • film refers to a thin, visually continuous material.
  • packing film refers to a thin, visually continuous material partially or completely emcompassing an object.
  • poly alpha-1 ,3-glucan is a polymer where the structure of poly alpha-1 ,3-glucan can be illustrated as follows (where n is 8 or more):
  • glucan formate refers to a derivatized form of poly alpha- 1 ,3-glucan where atleast one monomer in poly alpha-1 ,3-glucan has one or more hydroxyl groups of poly alpha-1 ,3-glucan that have reacted form a formate (-O-CHO), or may remain unreacted as a hydroxyl group.
  • This invention relates to poly alpha-1 ,3-glucan formate films and poly alpha-1 ,3-glucan films and the methods of their production from a polysaccharide poly alpha-1 ,3-glucan.
  • Poly alpha-1 ,3-glucan useful for certain embodiments of the disclosed invention, can be prepared using chemical methods.
  • poly alpha-1 ,3-glucan useful for certain embodiments of the disclosed invention can also be enzymatically produced from renewable resources, such as sucrose, using one or more glucosyl- transferase (e.g., gtfJ) enzyme catalysts found in microorganisms as described in the co-pending, commonly owned U.S. Patent Application Publication No. 2013/0244288 which is herein incorporated by reference in its entirety.
  • glucosyl- transferase e.g., gtfJ
  • a process for making a poly alpha-1 ,3-glucan formate film begins with dissolving poly alpha-1 , 3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate.
  • poly alpha-1 ,3-glucan is contacted with concentrated formic acid, one or more hydroxyl groups of poly alpha-1 ,3-glucan react to form a formate (-O- CHO).
  • the poly alpha-1 , 3-glucan formate thus formed dissolves in the same reaction mixture, resulting in a one-pot production of a casting solution composed of a derivatized polymer, starting with underivatized glucan and formic acid. The reaction proceeds even at room temperature.
  • cellophane raw material wood pulp
  • formic acid does not readily react with formic acid to produce cellulose formate.
  • This enhanced reactivity of poly alpha-1 ,3-glucan with formic acid offers significant advantages compared to cellulose esters like cellulose acetate.
  • Cellulose esters have to be synthesized in a separate reaction, the product has to be recovered, dried and then redissolved in a different solvent system to produce a solution for film casting. This is not required for the production of poly alpha-1 ,3-glucan formate.
  • the glucan monomer has 3 functional -OH groups that can be derivatized to form the formate ester. This gives a maximum degree of substitution (DoS) of 3.
  • the poly alpha-1 ,3-glucan is mixed into the solvent by application of shear to obtain clear solutions.At the initial stages of the reaction, the polymer granules swell. For high molecular weight polymer in solutions with polymer concentration of about 10 wt %, the swollen mixture has high viscosity and appears to be like a 'gel'. Over time, most likely due to increased derivatization of the polymer, the solubility of the polymer in formic acid increases and the polymer dissolves into the solution to form a clear, free-flowing solution.
  • the poly alpha-1 ,3-glucan is dissolved in the solvent composition at a concentration from about 5 wt % to about 20 wt %, more preferably about 6 wt % to about 15 wt % and most preferably about 7 wt % to about 10%.
  • the glucan monomer has 3 functional groups that can be derivatized with formate. It should be noted that the process of the invention can produce a poly alpha-1 ,3-glucan formate film with a DoS of formate of 3 or less depending on reaction conditions.
  • the DoS of formate comprises from at least about 0.1 to 3, preferably from at least about 0.2 to at most about 2.5, more preferably from at least about 0.3 to at most about 2.0 and most preferably from at least about 0.4 to about 1 .5.
  • the solubility of poly alpha-1 ,3-glucan formate in the solvent system is dependent on, in addition to other factors, the DoS as well as the composition of the solvent system. The lower the formic acid content in the solvent mixture, the longer the polymer takes to go into solution.
  • the kinetics for dissolution of the glucan polymer is dependent on the relative ratio of formic acid to glucan in the starting mixture, the shear rate during mixing as well as the water content of the starting mixture. It may also depend on the initial particle size. For example, an initial mixture
  • the degree of substitution of the polymer at this point is approximately 1 .6 to 1 .8.
  • an initial mixture composition of 6% polymer in a solvent composition of 80% formic acid, 20% water may take more than 40 hours to form a solution with overhead stirring.
  • the degree of substitution of the polymer at this time is approximately 0.9. It is believed that the polymer goes into solution once the degree of
  • substitution of the polymer is high enough such that it can dissolve in the solvent composition.
  • the rate of substitution depends on the initial solvent composition as well.
  • the solvent composition used to make the mixture comprises preferably at least about 80% formic acid and at most about 20% water and more preferably at least about 87% formic acid and at most about 13% water and most preferably at least about 90% formic acid and at most 10% water.
  • formation of solutions with solvent compositions below 80% formic acid may be possible, but since the rate of substitution will likely be reduced, longer dissolution times or increasing the rate of reaction by heat or increased shear may be needed.
  • the concentration of formic acid in the solution decreases while the concentration of water in the solution increases.
  • a polymer solution with solvent composition of 90% formic acid and 10% water can be achieved in three different ways, and the procedure used impacts the final solution and film properties.
  • the polymer is slurried in water, and formic acid is added to achieve a solvent mixture of 90% formic acid and 10% water.
  • a mixture composed of 90% formic acid and 10% water is prepared and the polymer is added to this mixture.
  • the polymer solution is made by using an intial solvent composition of 99.9% formic acid, mixing the polymeruntil dissolution and then adding water to achieve a final solvent of 90% formic acid and 10% water.
  • the differences in the solution and film properties are likely due to difference in intial dispersion of the polymer phase and differences in the degree and distribution of
  • the solution of poly alpha-1 ,3-glucan formate is contacted with a surface.
  • the films are produced by casting the solution onto a substrate using a rod coater or a draw down coater but can also be produced by other solution film casting methods such as extrusion through a slot die.
  • the substrates include but are not limited to glass (coated with or without surfactant).
  • the solvent composition is removed to form a poly alpha-1 ,3-glucan formate film.
  • the solvent composition may be removed by a series of steps that may include drying, coagulation, washing and subsequent air-drying followed by peeling the film off of the substrate.
  • the film may be heated.
  • the solvent composition can be removed by evaporation at room temperature or elevated temperature and at room pressure or reduced pressure. Further removal of formic acid solvent from the film may be obtained by washing the film with water.
  • the washed film is
  • the degree of substitution of the glucan formate groups can be decreased by soaking the film in dilute sulfuric acid, where the extent of the soak time and the concentration of the bath controls the reduction in the DoS.
  • the formyl groups may also be removed by heat treatment, such as by boiling in water or by other saponification methods such as treatment with dilute bases. It should be noted that depending on the solvent composition removal technique, some residual solvent composition or its' constituents may be present in small amounts. Thus some amount of residual formic acid and water may be left behind in the film.
  • the films thus obtained are clear and transparent.
  • the films with low formate content can be swollen by water. They can have a glossy or a matte appearance. They are flexible and exhibit good dead fold characteristics. They can be twisted and dyed.
  • the films can be used as packaging films.
  • One application of cellulose tri-acetate films is as protective layers for polarizer films for electronic applications.
  • Low birefringence in films is a critical property for this application. Refractive indices measurements on glucan formate films show that the in-plane birefringence of the films is about 0.005, while the out-of-plane birefringence is 0.002 or less. It is believed that the birefringence can be further reduced by change in film casting parameters.
  • poly alpha-1 , 3- glucan film can be made from poly alpha-1 , 3-glucan formate film by removing the formate.
  • the formate degree of substitution can be reduced by treating the film with sulphuric acid or by other methods such as saponification treatment with dilute bases or by wet heat. Submerging the films in aquous basic buffer solutions was found to reduce the DoS, here the extend of reduction depended on the pH and the soaking time.
  • the present invention is also directed toward a film comprising poly alpha-1 ,3-glucan formate and chitosan or chitosan formate.
  • chitosan refers to a family of copolymers, composed of two types of monomers as shown below
  • Chitosan is a polysaccharide made by deacetylating chitin, often derived from crusteacean shells. Chitosan is a random copolymer of beta-1 ,4-D-glucosamine and N-acetyl-D-glucosamine.
  • Chitosan is soluble in aqueous formic solutions and forms a solution over a wide range of compositions.
  • blend solutions containing both chitosan and poly alpha-1 ,3-glucan can be prepared in form ic acid.
  • the present invention is also directed toward a process for making a film of poly alpha-1 ,3-glucan formate and chitosan formate comprising: (a) dissolving poly alpha-1 ,3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate; (b) dissolving chitosan, either in dry form or as a pre-dissolved chitosan-formic acid solution, into the solution formed in part (a); (c) contacting the solution of poly alpha-1 ,3-glucan formate and chitosan formate with a surface; and (d) removing the solvent composition to form a film of poly alpha-1 ,3- glucan formate and chitosan formate.
  • the present invention is directed toward a film comprising poly alpha-1 ,3-glucan and chitosan.
  • the present invention is also directed toward a process for making a film of poly alpha-1 ,3-glucan and chitosan formate comprising: (a) dissolving poly alpha-1 ,3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate; (b) dissolving chitosan, either in dry form or as a pre-dissolved chitosan-formic acid solution, into the solution formed in part (a); (c) contacting the solution of poly alpha-1 ,3-glucan formate and chitosan with a surface; (d) removing the solvent composition to form a film of poly alpha-1 , 3-glucan formate and chitosan ; and (e) removing the formate in the film of poly alpha-1 ,3- glucan formate and chitosan to form the film of poly alpha-1 ,3-glucan and chitosan.
  • Chitosan is added to the solution by any convenient method. Being readily soluble in even dilute formic acid, chitosan could be predissolved and blended as a solution into another solution of poly alpha-1 , 3-glucan in formic acid. It could also added as a powder to a poly alpha-1 ,3-glucan solution in formic acid and then mixed in. The order of addition and the time that the two polymers are respectively exposed to higher
  • This invention relates to a film comprising poly alpha-1 ,3-glucan formate.
  • the poly alpha-1 ,3-glucan formate can have a formate degree of substitution (DoS) from about at least 0.1 to 3.
  • DoS formate degree of substitution
  • the film can have at least one of: (a) haze less than about 10%; and (b) tensile strength from about 10 to about 60 M Pa.
  • the film can further comprise chitosan formate.
  • the film can be used as a packaging film.
  • This invention also relates to a process for making a poly alpha-1 ,3- glucan formate film comprising: (a) dissolving poly alpha-1 ,3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate; (b) contacting the solution of poly alpha-1 ,3- glucan formate with a surface; and (c) removing the solvent composition to form a poly alpha-1 ,3-glucan formate film.
  • the poly alpha-1 ,3-glucan can be dissolved in the solvent composition at a concentration from about 5 wt % to about 20 wt %.
  • the solvent composition can comprise at least about 80% formic acid and at most about 20% water.
  • the solvent composition can be removed by: (a) evaporation at room temperature or elevated temperature and at room pressure or reduced pressure; (b) optionally rinsing the film with water; and (c) optionally repeating step (a).
  • the process can further comprise dissolving chitosan, either in dry form or as a pre-dissolved chitosan-formic acid solution, into the solution formed in part (a) dissolving poly alpha-1 ,3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate thereby forming a poly alpha-1 ,3-glucan formate and chitosan formate film in part (c).
  • the invention further relates to a film comprising poly alpha-1 ,3- glucan.
  • the film can further comprise chitosan.
  • the invention still further relates to a process for making a poly alpha-1 ,3-glucan film comprising: (a) dissolving poly alpha-1 ,3-glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate; (b) contacting the solution of poly alpha-1 ,3- glucan formate with a surface; (c) removing the solvent composition to form a poly alpha-1 ,3-glucan formate film; and (d) removing the formate in the poly alpha-1 ,3-glucan formate film to form the poly alpha-1 ,3-glucan film.
  • the poly alpha-1 ,3-glucan can be dissolved in the solvent composition at a concentration from about 5 wt % to about 20 wt %.
  • the solvent composition can comprise at least about 80% formic acid and at most about 20% water.
  • the solvent composition can be removed by evaporation at room temperature or elevated temperature and at room pressure or reduced pressure.
  • the formate in the poly alpha-1 ,3-glucan formate film can be removed by washing the poly alpha-1 ,3-glucan formate film with aqueous sulfuric acid, wet heating or by treatment with aqueous basic solutions.
  • the process can further comprise dissolving chitosan, either in dry form or as a pre-dissolved chitosan-formic acid solution, into the solution formed in part (a) dissolving poly alpha-1 ,3- glucan in a formic acid and water solvent composition to provide a solution of poly alpha-1 ,3-glucan formate thereby forming a poly alpha-1 ,3-glucan and chitosan film in part (d).
  • DPw Degree of Polymerization
  • PDI Polvdispersity Index
  • SEC Multidetector Size Exclusion Chromatography
  • Degree of Substitution was determined from 1 H nuclear magnetic resonance spectroscopy (NMR) and IR analysis. Approximately 10 mg of the polymer sample was weighed into a vial on an analytical balance. The vial was removed from the balance and 0.8 ml_ of deuterated trifluoroacetic acid was added to the vial. A magnetic stir bar was added to the vial and the mixture was stirred until the solid sample dissolves. Deuterated benzene (C6D6), 0.2 ml_, was then added to the vial in order to provide a better NMR lock signal than the TFA,d would provide. A portion, 0.8 ml_, of the solution was transferred, using a glass pipet, into a 5 mm NMR tube.
  • a quantitative 1 H NMR spectrum was acquired using an Agilent VnmrS 400 MHz NMR spectrometer equipped with a 5 mm Auto switchable Quad probe.
  • the spectrum was acquired at a spectral frequency of 399.945 MHz, using a spectral window of 6410.3 Hz, an acquisition time of 1 .278 seconds, an inter-pulse delay of 10 seconds and 124 pulses.
  • the time domain data was transformed using exponential multiplication of 0.78 Hz.
  • Two regions of the resulting spectrum were integrated; from 3.1 ppm to 6.0ppm, that gives the integral for the 7 protons on the poly alpha-1 ,3-glucan ring, and from 7.7 ppm to 8.4 ppm that gives the integral for the protons on the formate group.
  • the degree of substitution was calculated by dividing the formate protons integral area by one seventh of the poly alpha-1 ,3-glucan ring protons integral area.
  • the DRA-2500 is a 150 mm integrating sphere with a Spectralon® coating. Total and diffuse transmission for the instrument and the samples are collected over the wavelength range of 830 nm to 360 nm. The calculations are made in accordance with ASTM D1003 using a 2 degree observer angle and illuminant C (represents average daylight, color temperature 6700K).
  • Thickness of the film was determined using a Mitutoyo micrometer, No. 293-831 and reported in mm.
  • Oxygen Permeability was measured according to ASTM F 1927 at 75°F 0% RH and reported in cc/[m 2 -day].
  • Poly alpha-1 ,3-glucan using a gtfJ enzyme preparation was prepared as described in the co-pending, commonly owned U.S. Patent Application Publication No. 2013/0244288, which is incorporated herein by reference.
  • Formic acid was from Sigma Aldrich (St. Louis, MO). Sulphuric acid was obtained from EMD Chemicals (Billerica, MA).
  • the resulting film was clear, had a haze of 1 .5%, had a thickness of 0.019 mm and a tensile strength of 40 MPa.
  • the degree of substitution (DoS) of formate in the film measured using 1 H NMR was found to be 0.88.
  • Poly alpha-1 ,3-glucan with a DPw of 1050 was slurried in Dl water, then a mixture of formic acid in Dl water was added.
  • the final solution composition was 10 wt % polymer in a solution composition of 90% formic acid and 10% Dl water.
  • the solution was stirred and the viscosity increased significantly forming a thick gel-like consistency. The stirring was stopped and solution was left to stand until the viscosity of the solution had decreased and the solution was pourable.
  • a film was cast, air dried, soaked in water and air dried as in Example 1 a.
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 30 MPa, a maximum strain of 6.5% and a toughness of 1 .17 MPa.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 1 .26.
  • Poly alpha-1 ,3-glucan with a DPw of 1250 was mixed with a 90% solution of formic acid and Dl water.
  • the mixture composition was 10 wt % polymer, 81 % formic acid and 9% Dl water. The solution was stirred and the viscosity increased significantly forming a thick gel-like
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 40 MPa, a maximum strain of 13.1 % and a toughness of 36 MPa.
  • the DoS of formate in the film measured using 1 H NMR and was found to be1 .2 .
  • Example 2a The film of Example 2a was prepared in a similar manner to the film of Example 1 a except the film was treated with sulfuric acid to reduce the DoS of formate in the film. After the film was initially air dried but before soaking in a water bath as in Example 1 a, the film was soaked in a 5% sulfuric acid bath for 1 hour.
  • the resulting film was clear, had a thickness of 0.020 mm and a tensile strength of 35 MPa.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 0.43.
  • Example 2b Comparing the DoS of the films from Example 1 a and Example 2a demonstrated that the sulfuric acid treatment reduced the amount of formate in the film.
  • Example 2b Comparing the DoS of the films from Example 1 a and Example 2a demonstrated that the sulfuric acid treatment reduced the amount of formate in the film.
  • Example 2b The film of Example 2b was prepared in a similar manner to the film of Example 1 b.
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 30 MPa, a maximum strain of 6.0% and a toughness of 1 .20 MPa.
  • the degree of substitution (DoS) of formate in the film measured using 1 H NMR was found to be 1 .26.
  • the film was then divided into two halves. The first half was soaked in 5% sulfuric acid for 30 minutes. It was removed from the bath and washed in water. IR spectra was then obtained on the film and it was found that the substitution decreased by about 40% of the original substitution. The film was then returned to the sulfuric acid bath for an additional 30 minutes, then washed with water. Substitution decrease to about 50% of the starting formate measurement. The film was then soaked in sulfuric acid bath overnight. IR did not detect any formate substitution. The resulting film was clear, had a thickness of 0.023 mm, exhibited a tensile strength of 50 MPa, a maximum strain of 18% and a toughness of 4.9 MPa.
  • the second half of the film was then soaked in 10% sulfuric acid for 5 hours. It was removed from the bath and washed in water.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 0.28. Thus the DoS went down from 1 .26 before sulfuric acid soak to 0.28 after sulfuric acid soak.
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 33 MPa, a maximum strain of 1 1 % and a toughness of 2.1 MPa.
  • Poly alpha-1 ,3-glucan with a DPw of 550 was dissolved in 90% fornnic acid and 10% Dl water by stirring over night to make a 7 wt % polymer solution.
  • the solution was aged 24 hours.
  • a film was cast using a Chemlnstruments Custom Coater EC-300 and a 0.254 mm Meyer wire wound casting rod. The film was then immersed in a water bath for three days. Then the film was air dried. The film was soaked in 5% sulfuric acid for 4 minutes. The film was then rinsed in water several times until the pH of the rinse water remained neutral. Finally, the film was air dried.
  • the resulting film was clear, had a thickness of 0.015 mm.
  • the barrier properties of the film in terms of permeability to oxygen were measured.
  • the oxygen permeation rate was found to be 9.25 cc/[m 2 -day].
  • Example 4a was prepared in a similar manner to the film of Example 3a. Films prepared by this technique may have residual formic acid content of about 5 wt% as well as residual water content. The film was heated from 30°C to 250°C at 5°C/minute followed by a 5 minute hold at 250°C.
  • Poly alpha-1 ,3-glucan with a DPw of 1250 was mixed with a 95% solution of formic acid and Dl water.
  • the final solution composition was 7.5 wt % polymer, 88% formic acid and 4.5% Dl water.
  • the solution was stirred and the viscosity increased significantly forming a thick gel-like consistency. The stirring was allowed to continue for 22 hours during which the solution viscosity decreased and the solution became pourable. Films were cast, coagulated in water, rinsed 3 times with water and air dried.
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 37.6 MPa and a maximum strain of 7.26%.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 1 .34.
  • the NMR spectra also showed presence of residual formic acid in the film.
  • the film was then boiled in water for 3 hours.
  • the film remained clear, had a thickness of 0.024 mm, a tensile strength of 20.7 MPa and a maximum strain of 7.37%.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 0.65. This demonstrates that formate content of the film may be reduced by boiling in water, particularly in the presence of residual formic acid.
  • Poly alpha-1 ,3-glucan with a DPw of 800 was mixed with a 90% solution of formic acid and Dl water.
  • the final solution composition was 10 wt % polymer, 81 % formic acid and 9% Dl water. The solution was stirred and the viscosity increased significantly forming a thick gel-like
  • the resulting film was clear, had a thickness of 0.024 mm, a tensile strength of 70.9 MPa and a maximum strain of 17.5%.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 1 .28.
  • the film was then placed in a buffer solution of pH 10 for 18 hours. The film was rinsed with water and allowed to air dry.
  • the resulting film was clear, had a thickness of 0.024 mm, a tensile strength of 63.7 MPa and a maximum strain of 26.1 %.
  • Another film with an initial DoS of 1 .1 was soaked in a buffer solution of pH 10 for 18 hours. The film was rinsed with water and allowed to air dry.
  • the DoS of formate in the film measured using 1 H NMR and was found to be O.This demonstrates that formate content of the film may be reduced by treatment with a base.
  • Poly alpha-1 ,3-glucan with a DPw of 800 was mixed with a 95% solution of formic acid and Dl water.
  • the final solution composition was 10 wt % polymer, 85.5% formic acid and 4.5% Dl water.
  • the solution was stirred and the viscosity increased significantly forming a thick gel-like consistency. The stirring was allowed to continue for 21 hours during which the solution viscosity decreased and the solution became pourable.
  • a film was cast on glass, coagulated in water until it remained neutral and air dried. The resulting film was clear.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 1 .47.
  • Poly alpha-1 ,3-glucan with a DPw of 1050 was slurried in Dl water, then a mixture of formic acid in Dl water was added.
  • the final solution composition was 10 wt % polymer in a solution composition of 90% formic acid and 10% Dl water.
  • the solution was stirred and the viscosity increased significantly forming a thick gel-like consistency. The stirring was stopped and solution was left to stand for 20 days. After which time, the viscosity of the solution had decreased and the solution was pourable.
  • the solution viscosity was estimated by noting the solution level in the centrifuge tube, inverting the tube and measuring time for solution to reach the 45ml mark on the tube. The time for this solution was measured to be 1 sec.
  • the resulting film was clear, had a thickness of 0.033 mm, maximum strain of 5.9%, and a tensile strength of 50 MPa.
  • the resulting film was clear, had a thickness of 0.023 mm, a tensile strength of 33 MPa, a maximum strain of 5.1 %.
  • the DoS of formate in the film measured using 1 H NMR and was found to be 0.97.

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Abstract

La présente invention concerne un procédé de fabrication de films de poly alpha-1,3-glucane formiate. Ces films sont translucides ou transparents et sont utilisables dans des applications d'emballage.
PCT/US2015/011551 2014-01-17 2015-01-15 Production de films de poly alpha-1,3-glucane formiate Ceased WO2015109066A1 (fr)

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WO2015200605A1 (fr) * 2014-06-26 2015-12-30 E. I. Du Pont De Nemours And Company Production de boyaux alimentaires à base de poly alpha-1,3-glucane formaite
WO2015200593A1 (fr) * 2014-06-26 2015-12-30 E.I. Du Pont De Nemours And Company Production de films en poly(alpha-1,3-glucane) formiate
WO2015200596A1 (fr) * 2014-06-26 2015-12-30 E. I. Du Pont De Nemours And Company Préparation de films d'ester de poly alpha-1,3-glucane
US10059778B2 (en) 2014-01-06 2018-08-28 E I Du Pont De Nemours And Company Production of poly alpha-1,3-glucan films
WO2018200437A1 (fr) * 2017-04-25 2018-11-01 E. I. Du Pont De Nemours And Company Revêtements polysaccharidiques présentant des propriétés de barrière à l'oxygène
US10731297B2 (en) 2015-10-26 2020-08-04 Dupont Industrial Biosciences Usa, Llc Water insoluble alpha-(1,3-glucan) composition
US10738266B2 (en) 2015-06-01 2020-08-11 Dupont Industrial Biosciences Usa, Llc Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan
US10800859B2 (en) 2014-12-22 2020-10-13 Dupont Industrial Biosciences Usa, Llc Polymeric blend containing poly alpha-1,3-glucan
US10822574B2 (en) 2015-11-13 2020-11-03 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10844324B2 (en) 2015-11-13 2020-11-24 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10876074B2 (en) 2015-11-13 2020-12-29 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10895028B2 (en) 2015-12-14 2021-01-19 Dupont Industrial Biosciences Usa, Llc Nonwoven glucan webs
US11230812B2 (en) 2015-10-26 2022-01-25 Nutrition & Biosciences Usa 4, Inc Polysaccharide coatings for paper
US11351104B2 (en) 2015-02-06 2022-06-07 Nutrition & Biosciences USA 4, Inc. Colloidal dispersions of poly alpha-1,3-glucan based polymers

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WO2015200593A1 (fr) * 2014-06-26 2015-12-30 E.I. Du Pont De Nemours And Company Production de films en poly(alpha-1,3-glucane) formiate
WO2015200596A1 (fr) * 2014-06-26 2015-12-30 E. I. Du Pont De Nemours And Company Préparation de films d'ester de poly alpha-1,3-glucane
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